Alkyl urea-formaldehyde resin



Patented l=b.,.I7, 1942 ICE ALKYL UREA-FORMALDEHYDE RESIN John F. Olin, Grosse Ile, Mich assignor to Sharples Chemicals Inc., a corporation of Delaware No Drawing. Application January 30, 1940, Serial No. 316,315

14 Claims.

This application is a continuation in part of my prior application, Serial Number 164,525, filed September 18, 1937, for Manufacture of resins.

The present invention relates to the art of synthetic resins and to the formation of resins of the general type produced by condensation of urea and its derivativeswith formaldehyde or its equivalent, such as paraformaldehyde, tri-oxymethylene, or hexamethylene tetramine.

Itis a well-known fact that urea may be reacted with formaldehyde to produce condensation products. This reaction may be greatly accelerated by the use of small amounts of acids as catalysts and it may also be accelerated with the aid of alkaline catalysts. The resulting condensation products may be converted into hard, solid resins by the application of heat to remove water and excess formaldehyde and cause further polymerization.

The resulting resins are valuable in commerce because of their pale color and transparency and the fact that they may be molded into various useful shapes. Their relative insolubility in organic solvents, however, limits their utility in coating compositions. When higher alkyl ureas such as butyl area, amyl area, hexyl urea, heptyl urea, cyclohexyl urea, etc., are condensed with formaldehyde in accordance with the method discussed above, the resulting condensation products are soluble in certain organic solvents but theycannot ordinarily be solidified by the action of heat in the manner in which resins produced from urea, thio-urea or the lower homologues of urea such as methyl urea and ethyl ureacan be solied. I

An object of the present invention has been to produce a solid condensation product of the general type of that produced by condensation of an indefinite period of time. When a small prourea with formaldehyde, which has the advantages of the condensation products obtained by condensing butyl urea with formaldehyde, for example, in that it is soluble in organic solvents such as amyl alcohol, but retains the advantageous properties of the condensation product of urea with formaldehyde in that it can be soliditied by the application of heat.

The present invention rests upon the discovery that condensation products obtained by condensing with aldehydes alkyl ureas having four or more carbon atoms in the alkyl radical may be solidified by the application of heat provided a sufficient proportion of urea or one of the'lower alkyl homologues thereof (such as methyl or ethyl urea) is condensed with the aldehyde in the same reaction in which the higher alkyl urea is portion of urea is mixed with amyl urea, however, and the mixture of urea and amyl urea is condensed with formaldehyde in the presence or absence of an acid or basic catalyst, the resulting condensation product may be heated todrive ofi water and formaldehyde, and the further applicationof heat will cause polymerization of the condensate to produce a solid, transparent resin which is soluble in amyl alcohol. Similarly advantageous results may be obtained by condensing other higher alkyl ureas such as butyl urea, hexyl urea, heptyl urea, octyl urea and cyclohexyl urea, with 'aldehydes in the presence of relatively small proportions of urea, methyl urea, I

ethyl urea or thio urea.

Solid resins may be produced by condensing tertiary alkyl ureas or cyclohexyl urea with formaldehyde, without incorporating any urea, methyl urea, or ethyl urea in the reaction mixture. Even in the case of resins produced from these derivatives, however, it is desirable that some urea, methyl urea or ethyl urea be condensed with formaldehyde along with the higher alkyl urea in order to produce a harder resin than would otherwise be attainable from the tertiary alkyl or cyclohexyl urea.

Example I Butyl ammonium chloride was refluxed with urea in water solution to produce a monobutyl urea. 20 grams of the butyl urea so produced were mixed with 10. grams of. urea and with 45 grams of formaldehyde. 0.5 gram of hydrochloric acid was added to the reaction mixture and the reaction was allowed to proceed for a period of 15 minutes. The viscous oil layer was separated and was then heated to a temperature of C. for a period of 24 hours. At the conclusion of this heating step, the condensation product was a hard, horny, transparent resin of light color. This resin was found to be soluble in alcohols having 1-6 carbon atoms.

. face.

Example II 20 grams of butyl urea were mixed with 5 grams of urea and with 45 grams of formaldehyde. The mixture was condensed in the same manner as in Example I. The condensation reaction produced a tough, colorless, slightly tacky resin which was easily soluble in alcohols of 1-6 carbon atoms. The alcohol solution was found to be soluble in nitro cellulos solution. The homogeneous lacquers so produced do not require plasticizers and films produced by application of said lacquers adhere excellently to a coated sur- Example III 20 grams of butyl urea were mixed with grams of thio urea in 10 grams of hot water. 45 grams of formaldehyde were added and the mixture was condensed in the presence of hydrochloric acid in the same manner as in Example I. The resulting resin was found to be soluble in alcohols of l-6 carbon atoms.

In the practice of the invention, it is not entirely essential that the higher alkyl urea and urea or lower alkyl urea be mixed with each other and with the formaldehyde at the very start of the condensation reaction. The invention may be practiced by partially condensing either urea constituent with formaldehyde and introducing the other urea constituent at an intermediate stage of the condensation reaction.

As a still further alternative, the urea or lower alkyl urea may be condensed with formaldehyde to an intermediate stage, and the higher alkyl urea may be condensed to a similar stage in a separate reaction. The two partial condensation reaction products may then be combined for further condensation and hardening in a single final operation. a

While the invention has been-discussed above in terms of production of solid resins, urea and lower alkyl urea derivatives may be combined with alkyl urea derivatives containing at least four substitutent carbon atoms in the practice of the invention to produce products which are not solid resins, but are viscous liquids, falling within the scope of the invention. These viscous liquids have value as plasticizers and adhesives. The inclusion of a higher proportion of urea or lower alkyl urea in the reaction mixture tends to give the ultimate condensation product, after heat treatment to attain the solid form, increased solidity and hardness. Increasing the proportion of the higher alkyl urea, on the other hand, tends to produce a softer resin, in case a solid resin is produced, ortends to produce a viscous liquid condensation product instead of a solid resin, in case the proportion of the higher alkyl urea is very high. From the above discussion, persons skilled in the art will be able to produce either a solid resin or a viscous liquid condensation product having value as an adhesive or plasticizer, depending upon the relative proportions of the higher alkyl urea and urea or lower alkyl urea, respectively, employed in the condensation reaction.

Modifications will be obvious to those skilled in the art, and I do not therefore wish to be limited except by the scope of the sub-joined claims.

I claim:

1. A condensation product formed by the condensation reaction with formaldehyde of a mixture of an unsubstituted urea and a urea substituted by an alkyl radical containing at least four carbon atoms, said unsubstituted urea being 75 present in the condensation reaction in an amount sufllcient to permit the final product to be hardened by the application of heat, and said higher aikyl substituted urea being present in the con- 5 densation reaction in an amount sufiicient to enable the final product to be dissolved in organic solvents.-

2. A condensation product as described in claim 1 in which the mixture of unsubstituted i0 urea and higher alkyl substituted urea contains at least sixteen and two-thirds per cent by weight of unsubstituted urea.

3. A process of producing condensation products which comprises condensing with formaldehyde a mixture of an unsubstituted urea and a urea substituted by an alkyl radical containing at least four carbon atoms, said unsubstituted urea constituting at least sixteen and two-thirds per cent by weight of the mixture of unsubstituted urea and higher alkyl substituted urea.

4. A condensation product formed by the condensation reaction with formaldehyde of a mixture of an unsubstituted urea and a urea substituted by an alkyl radical containing at least four carbon atoms, said unsubstituted urea being present in the condensation reaction in an amount sumcient to permit the final product to be solidified by the application of heat, and said higher alkyl substituted urea being present in the condensation reaction in an amount sufllcient to enable the final product to be dissolved in organic solvents.

5. A condensation product formed by the condensation reaction with formaldehyde of a mixture of (l) a substance selected from the class consisting of urea, thiourea, methyl urea, and

I ethyl urea; and (2) a urea substituted by an alkyl radical containing at least four carbon atoms; the substance selected from said class being present in the condensation reaction in an amount sufiicient to permit the final product to be hardened by the action of heat, and the higher alkyl substituted urea (2) being present in the condensation reaction in an amount sufiicient to enable the final product to be dissolved in organic solvents.

6. A condensation product as described in claim 5 in which the mixture of ureas contains at least 16% per cent by weight of the substance selected from the class consisting of urea, thiourea, methyl urea and thyl urea.

'7. A process of producing condensation products that comprises condensing with formaldehyde a mixture of: (1) a substance selected from the class consisting of urea, thiourea, methyl urea, and ethyl urea; and (2) a urea substituted by an alkyl radical containing at least four carbon atoms; the said selected substance (1) constituting at least 16% per cent by weight of the urea mixture.

8. A condensation product formed by the condensation reaction with formaldehyde of a mixture of (l) a substance selected from the class consisting of urea, thiourea, methyl urea, and

ethyl urea; and (2) a urea substituted by an alkyl radical containing at least four carbon atoms; said selected substance (1) being present in the condensation reaction in an amount sufiicient to permit the final product to be solidified by the application of heat, and said higher alkyl substituted urea (2) being present in the condensation reaction in an amount sufficient to enable the final product to be dissolved in organic solvents.

9. Heat-hardenable condensation products garages characterized by being soluble in alcohols having one to six carbon atoms formed bycondensing formaldehyde with a mixture consisting of (1) alkyl ureas wherein the alkyl substituent contains a minimum of four carbon atoms, and (2) a substance selected from the class consisting of urea, thiourea, methyl urea, and ethyl urea.

10. A process of producing condensation products that comprises condensing with formaldehyde a mixture of: (l) a substance selected from the class consisting of urea, th'iourea, methyl urea, and ethyl urea, present in the condensation reaction in an amount sufilcient to permit the final product to be hardened by heat treatment;

pared by the process described inclaim 10.

13. A process of producing condensation products that comprises condensing with formaldehyde at least two diiferent urea compounds, one

'of which is selected from the class consisting of urea, thiourea, methyl urea and ethyl urea, and the other'is a higher alkyl substituted urea containing at least four substituent alkyl carbon atoms, one of said urea compounds being initially reacted with formaldehyde to form a condensation product which is thereafter reacted with the other urea compound to form the flanl condensation product.

14. In the manufacture of condensation prod ucts of formaldehyde with urea and derivatives thereof, the process that comprises condensing with formaldehyde at least two urea compounds of which one is chosen from the class consisting of thiourea, methyl urea, and ethyl urea, and the other urea compound is analkyl substituted urea containing at least foursubstituent alkyl carbon atoms, by condensing the urea compound of one of the mentioned classes with formaldehyde to form a liquid condensation 

